Metal or metal compound pattern and forming method of pattern, and electron emitting device, electron source, and image-forming apparatus using the pattern

ABSTRACT

The present invention is to provide a method for forming various patterns such as a metal or metal compound pattern, in which the amounts of the materials constituting the pattern which are removed during the formation step can be suppressed to the minimum. The method comprises a resin pattern forming step of forming on the surface of a substrate a resin pattern capable of absorbing a solution containing metal components, an absorbing step of dipping the resin pattern in the solution containing metal components to make the resin pattern absorb the solution containing metal components, a washing step of washing the substrate having formed thereon the resin pattern that has absorbed the solution containing metal components, and a burning step of burning the resin pattern after washing.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for forming a metal or metalcompound pattern by using a solution containing metal components, and amethod for manufacturing an electron emitting device, an electron sourceand an image-forming apparatus using the pattern. The present inventionalso relates to a metal or metal compound pattern using a desiredporosity; and an electron emitting device, an electron source and animage-forming apparatus using the pattern.

2. Related Background Art

With respect to a method for forming an electrically conductive patternused as an electrode, a wiring and the like, conventionally known arethe following methods: (1) a method of adhering a metal by a sputteringmethod (by a sputtering), patterning a resist and performing etching byan ion-milling method to peel a resist; (2) a method of printing anelectrically conductive paste to a desired pattern using a screenprinting, and then drying/baking it to form a desired electricallyconductive pattern; (3) a method of forming an electrically conductivepattern by transfer; (4) a method of coating an electrically conductivepaste over the entire surface of a substrate, drying/baking it to form ametal film, covering a desired part of the metal film with a mask suchas photo resist and etching the parts other than the desired parts toform a desired electrically conductive pattern; (5) a method ofimparting the photosensitivity to a metal paste, exposing a desired partthereof and then developing it to form an electrically conductivepattern (Japanese Patent Application Laid-open No. 5-114504); and (6) amethod of allowing a layer formed of gelatin or the like to absorbdroplets having electroconductivity and burning-removing the gelatinlayer to form an electroconductive film (Japanese Patent ApplicationLaid-open No. 9-213211).

However, the method (4) and the method (5) have a problem in that,particularly in a case of constituting an electrically conductivepattern by a noble metal such as platinum, a large amount of noble metalcomponents are removed at the time of etching and development, whichresults in much labor and a heavy burden in terms of equipment requiredfor recovering and reusing the components removed. Also, there arisesthe above-described problem not only in the formation of an electricallyconductive pattern but also in the formation of a metal compound patternincluding insulating materials. Accordingly, a solution for this problemhas been demanded.

With respect to the quality of the formed pattern, the film patternformed according to the method (1) has high film density and electrodeproperties of the pattern itself have no problem. However, it has aproblem that in the presence of dissimilar metals, the propertiesthereof change with the passage of time because dissimilar metals easilydiffuse and move. Further, in the electron emitting device, thediffusion of dissimilar metals may adversely affect the electronemitting property, which is regarded as a problem (Japanese PatentApplication Laid-open No. 2000-243327). Further, the film patternsformed according to the methods (2) to (5) have low film densities andit is difficult to stably control the film quality. Therefore, forexample, when a plurality of patterns are formed on a substrate, therearises a problem that uneven distribution takes place with respect tothe electrical properties.

In particular, according to the method (2), it was difficult to form afine pattern. According to the method (3), it was difficult to form apattern having a uniform film quality or to form a pattern havingreproducibility.

SUMMARY OF THE INVENTION

The present invention has been made by taking account of these problemsinherent in conventional techniques and the object of the presentinvention is to provide a method for forming various patterns such as ametal or metal compound pattern, in which the amounts of the materialsconstituting the pattern which are removed during the formation step canbe suppressed to the minimum, and in particular, even when a pattern isconstituted by a noble metal such as platinum, the materialsconstituting the pattern which are removed during the formation step canbe recovered and reused at the minimum load.

Another object of the present invention is to provide a metal or metalcompound pattern, in particular, preferably an electrode pattern, inwhich the stability of properties as a metal or metal compound patternare maintained and at the same time, the diffusion and movement ofdissimilar metals in the presence of dissimilar metals is suppressed.

According to the present invention, there is provided a method ofmanufacturing a metal or metal compound pattern, the method comprising:a resin pattern forming step of forming on the surface of a substrate aresin pattern capable of absorbing a solution containing metalcomponents; an absorbing step of dipping the resin pattern in thesolution containing metal components to make the resin pattern absorbthe solution containing metal components; a washing step of washing thesubstrate having formed thereon the resin pattern that has absorbed thesolution containing metal components; and a burning step of burning theresin pattern after washing.

Further, according to the present invention, there is provided a methodof manufacturing a metal or metal compound pattern, the methodcomprising: a resin pattern forming step of forming on the surface of asubstrate a resin pattern capable of absorbing a solution containingmetal components; an absorbing step of coating the solution containingmetal components onto the resin pattern by a spray method or a spin coatmethod to make the resin pattern absorb the solution containing metalcomponents; a washing step of washing the substrate having formedthereon the resin pattern that has absorbed the solution containingmetal components; and a burning step of burning the resin pattern afterwashing.

Still further, according to the present invention, there is provided amethod of manufacturing a metal or metal compound, the methodcomprising: a resin pattern forming step of forming on the surface of asubstrate a resin pattern capable of absorbing a solution containingmetal components and capable of ion-exchanging the metal components; anabsorbing step of making the resin pattern absorb the solutioncontaining metal components; and a burning step of burning the resinpattern that has absorbed the solution containing metal components.

Further, according to another aspect of the present invention, there isprovided a pattern comprising: a first region having a first metal or afirst metal compound and having a porosity of 60% or less; and a secondregion disposed so as to be in contact with the first region and havinga second metal or a second metal compound which is different from thefirst metal or the first metal compound.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of the device electrode pattern formed inExample 3 and Example 15; and

FIG. 2 is a schematic view showing a display panel portion of theimage-forming apparatus manufactured in Example 3 and Example 15.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides a method of forming a pattern in which aresin patterned on a substrate is absorbed by-dipping it in a solutioncontaining metal components or by coating thereon a solution containingmetal components, and then the substrate is washed to form thereon apattern through a burning step. The present invention also provides amethod of forming a pattern in which the above-mentioned solutioncontaining the metal components is absorbed in a resin pattern capableof absorbing a solution containing metal compounds and capable ofion-exchanging the metal components, and then burning the resin pattern.In particular, the present invention provides a method of forming ametal or metal compound pattern by using a photosensitive resin and asolution containing metal components. Representative examples of themetal or metal compound pattern formed according to the presentinvention include an electrode, a wiring and an insulating layercomposed of a metal oxide. Of the metal or metal compound patternsformed according to the present invention, the forming method of anelectrically conductive pattern is useful, for example, for amanufacturing method of an electron emitting device having an electrode,for a manufacturing method of an electron source having a plurality ofthis electron emitting devices, and particularly for alleviating theburden of recovering and reusing the constituent materials in amanufacturing method of an image-forming apparatus using this electronsource.

According to another aspect of the present invention, there is provideda pattern comprising: a first region having a first metal or the firstmetal compound and having a porosity of 60% or less; and a second regiondisposed so as to come into contact with the first region and having asecond metal or a second metal compound which is different from thefirst metal or the first metal compound.

By virtue of the above arrangement, in the first region and the secondregion, for example, used as a device electrode constituting an electronemitting device, the constitution materials of a wiring connecting withthe above-described device electrode is prevented from diffusing and anelectron emitting device having preferable properties can be provided.

In the present invention, the term metal means a metal including even analloy. The above description that “The first metal or the first metalcompound is different from the second metal or the second metalcompound” also refers to a case where these are composed of the sameelement but the ratio thereof is different.

For example, when each of the first region and the second region isconstituted by a solder as an alloy of tin (Sn) and lead (Pb) at theratio of Sn:Pb=7:3, and Sn:Pb=6:4, respectively, then the first regionand the second region are different from each other and these are withinthe scope of the present invention. Also, when the first region and thesecond region are constituted using a mixed paste of silver (Ag) andlead oxide (PbO) used for a wiring, while varying the mixed ratiothereof between the first and second regions, the first region and thesecond region are different from each other.

As described above, the present invention may be applied to an electronemitting device and an image-forming apparatus using the device.Examples of the electron emitting device include a surfaceconductive-type electron emitting device in which an electricallyconductive thin film is formed to connect with a pair of deviceelectrodes that are formed so as to oppose with each other on anelectrically insulating substrate, and then this electrically conductivethin film is subjected to a welding treatment referred to as a formingto locally destroy, deform or alter the electrically conductive thinfilm to thereby form a part having electrically high resistanceincluding a crack, and which uses a phenomena that after forming thepart having electrically high resistance including a crack, if a voltageis applied between the device electrodes and a parallel electric currentis applied onto the surface of the electrically conductive thin film, anelectron emission occurs through the part having electrically highresistance including the crack (electron emitting part). Other examplesthereof include an electric field emitting-type electron emitting devicereferred to as “FE-type” or an electron emitting device having ametal/insulating layer/metal-type structure referred to as “MIM-type”.

Examples of an electron source provided with a plurality of electronemitting devices and a wiring for driving a plurality of the electronemitting devices include an electron source having electron emittingdevices disposed in a ladder-like fashion, in which a plurality ofelectron emitting devices having a pair of device electrodes aredisposed in a matrix form in an X direction and a Y direction, onedevice electrode and another device electrode of a plurality of theelectron emitting devices, which are disposed in the same line, areconnected to a common wiring and in which, at the same time, an electronfrom the electron emitting devices can be control-driven by an controlelectrode (also referred to as “a grid”) disposed above the electronemitting devices in the orthogonal direction to this wiring.

Another example of the electron source include an electron source inwhich a plurality of the electron emitting devices are disposed in amatrix form in an X direction and a Y direction, and one deviceelectrode of a plurality of the electron emitting devices that aredisposed in the same line is connected to a common wiring in the Xdirection and another device electrode of a plurality of the electronemitting devices disposed in the same line is connected to a commonwiring in the Y direction. This is a so-called simple matrixarrangement.

Examples of an image-forming apparatus include those manufactured bycombining the electron source as described above with image-formingmembers forming an image by the irradiation of an electron beam emittedfrom an electron emitting device of this electron source. If animage-forming member having a fluorescent material emitting a visibleradiation by an electron is used, a display panel that may be used as atelevision or computer display can be fabricated. If a photosensitivedrum is used as an image-forming member and a latent image is formed onthis photoreceptor drum by the irradiation of an electron beam can bedeveloped using toner, a copy machine or a printer can be manufactured.

With respect to the preferred embodiments of the present invention,materials used (a solution containing a resin and metal components), themethod of forming the metal or metal compound pattern, in particular,the electrically conductive pattern of the present invention, acalculation method of the porosity, and the manufacturing method of theelectron emitting device, the electron source, and the image-formingapparatus of the present invention are described in sequence below.

(1) Photosensitive Resin

The resin for use in the present invention is preferably aphotosensitive resin and is not particularly limited as long as theresin pattern formed using the photosensitive resin can absorb asolution containing metal components that is described later. Both awater-soluble photosensitive resin and a solvent-soluble photosensitiveresin may be used. The term “A water-soluble photosensitive resin”refers to a photosensitive resin that allows a development in thedevelopment step described later to be performed with water or adeveloper containing at least 50% by weight of water. The term “Asolvent-soluble photosensitive resin” refers to a photosensitive resinthat allows a development in a development step to be performed with anorganic solvent or a developer containing at least 50% by weight of anorganic solvent.

The photosensitive resin may be a resin having a photosensitive group inthe resin structure or may be a resin having mixed therein aphotosensitive agent such as cyclized rubber-bisazide resist. In eitherphotosensitive resin component, a photoreaction initiator or aphotoreaction inhibitor may be mixed as appropriate. The photosensitiveresin may be a type (a negative type) that a photosensitive resincoating soluble in a developing solution turns to be insoluble in adeveloping solution by the photoirradiation or may be of a type (apositive type) in which a photosensitive resin coating insoluble in adeveloping solution turns to be soluble in a developing solution by thephotoirradiation.

In the present invention, a general photosensitive resin can be used ina wide range as described above. Particularly preferred is anion-exchangeable resin reacting with metal components in a solutioncontaining metal components that is described later. A water-solublephotosensitive resin is also preferably used because a preferable workenvironment can be easily maintained and the resulting waste scarcelyputs a load on nature.

The water-soluble photosensitive resin will be further described. Thiswater-soluble photosensitive resin may be a resin which uses a developercontaining at least 50% by weight of water and having added thereto alower alcohol such as methyl alcohol or ethyl alcohol for increasing thedrying rate or a component for attaining the dissolution acceleration orthe stability improvement of the photosensitive resin components, withinthe range of less than 50% by weight. From the standpoint of reducingthe environmental load, however, preferred is a resin that allows adevelopment with a developer having a water content of 70% by weight ormore, more preferred is a resin that allows a development with adeveloper having a water content of 90% by weight or more and mostpreferred is a resin that allows a development using only water as adeveloper. Examples of this water-soluble photosensitive resin include aresin comprising a water-soluble resin such as polyvinyl alcohol resinor polyvinyl pyrrolidone resin.

(2) Solution Containing Metal Components

The solution for use in the present invention is preferably a solutioncontaining metal components. In this case, the solution may be anorganic solvent-type solution comprising an organic solvent-type solventcontaining 50% by weight or more of an organic solvent or may be anaqueous solution comprising an aqueous solvent containing 50% by weightor more of water, as long as it can form a metal or metal compound filmby burning. For such a solution containing metal components, forexample, there can be used a solution obtained by dissolving as metalcomponents an organic solvent-soluble or a water-soluble metal organiccompound formed of platinum, silver, palladium or copper in an organicsolvent-type solvent or an aqueous solvent. Among these, a solution inwhich a platinum organic compound is dissolved is preferably usedbecause an electrically conductive pattern which is very chemicallystable can be easily obtained.

Similarly to the above-described photosensitive resin, the solutioncontaining metal components for use in the present invention ispreferably an aqueous solution because a preferable work environment canbe easily maintained and the resulting waste scarcely puts a load onnature. The aqueous solvent for this aqueous solution may be an aqueoussolvent containing 50% by weight or more of water and having addedthereto, for example, a lower alcohol such as methyl alcohol or ethylalcohol for accelerating the drying rate or having added thereto acomponent for achieving the dissolution acceleration or the stabilityimprovement of the above-described metal organic compound, within therange of less than 50% by weight. From the standpoint of reducing theenvironmental load, however, the water content of the solvent ispreferably 70% by weight or more, more preferably 90% by weight or more,and most preferably, the solvent is all water.

Examples of a water-soluble metal organic compound which can form anelectrically conductive film particularly by burning include a complexcompound of gold, platinum, silver, palladium, copper or the like.

The complex compound is preferably the one such that the ligand thereofis constituted by a nitrogen-containing compound having at least onehydroxyl group in a molecule. Among the complex compounds in which theligand thereof is constituted by a nitrogen-containing compound havingat least one hydroxyl group in a molecule, preferred is, for example, acomplex compound such as alcoholamine, (ethanolamine, propanolamine,isopropanolamine and butanolamine or the like), selinenol and TRIS, inwhich the ligand thereof is constituted by any one ofnitrogen-containing compounds having 8 or less carbon atoms or by two ormore thereof.

The reasons why the complex compound is preferably used include its highwater-solubility and low crystallinity. For example, in a commerciallyavailable amine complex, a crystal precipitates during the drying and anuniform film is hardly obtained in some cases. If a “flexible” ligandsuch as those constituted by aliphatic alkylamine is used, thecrystallinity can be lowered but the water-solubility may decrease dueto hydrophobic property of an alkyl group. On the other hand, if acomplex compound wherein the ligand is constituted as described above isused, a high water-solubility and a low-crystallinity may be obtained atthe same time.

For the purpose of improving the film quality of the electricallyconductive pattern obtained and improving the adhesion of theelectrically conductive pattern to a substrate, for example, an elementform such as rhodium, bismuth, ruthenium, vanadium, chromium, tin, leadand silicon or a compound thereof is preferably contained as a componentof the above-described metal compound.

(3) Method of Forming Electrically Conductive Pattern

The formation of the electrically conductive pattern according to thepresent invention can be performed through the resin pattern formingsteps as described below (coating step, drying step, exposing step anddeveloping step), absorbing step, washing step, burning step, ifdesired, milling step.

The coating step is a step for coating the above-describedphotosensitive resin on an insulating substrate on which an electricallyconductive pattern is to be formed. This coating can be performed usingvarious printing methods (screen printing, off-set printing,flexographic printing), spinner method, dipping method, spray method,stamp method, rolling method, slit coater method, ink jet method or thelike.

The drying step is a step for vaporizing a solvent in a photosensitiveresin film that has been coated on the substrate in the above-describedcoating step to thereby dry the coating. The coating film can be driedat a room temperature but preferably dried through heating forshortening the drying time. The drying by heating can be performedusing, for example, a no-wind oven, a dryer or a hot plate and can begenerally performed by placing the film under a temperature of 50 to100° C. for 1 to 30 minutes, though the conditions vary depending on theformulation or coating amount of the composition coated for forming anelectrode and a wiring.

The exposing step is a step for exposing the photosensitive resin filmon the substrate, which was dried in the above-described drying step,according to the predetermined resin pattern (for example, apredetermined shape of an electrode or a wiring). The region to beexposed by the photoirradiation in the exposing step varies depending onwhether the photosensitive resin used is a negative-type resin or apositive-type resin. In the case of a negative-type resin that becomesinsoluble in a developing solution by the photoirradiation, an exposureis performed by irradiating light to the region to be left as a desiredresin pattern. On the other hand, in the case of a positive-type resinthat becomes soluble in a developing solution by the photoirradiation,contrary to a negative-type resin, an exposure is performed byirradiating light to the region other than the region to be left as aresin pattern. The photoirradiation region and the non-irradiationregion can be selected in the same manner as performed in a general maskformation by photoresist.

The developing step is a step for removing the photosensitive resin filmin the region other than the region to be left as a desired resinpattern, in the photosensitive resin film that was exposed in theabove-described exposing step. When the photosensitive resin is anegative type resin, a photosensitive resin film in the region where thephotoirradiation was not performed is soluble in a developing solutionand a photosensitive resin film in the region exposed byphotoirradiation is made insoluble in a developing solution. Therefore,a development can be performed by dissolving and removing with adeveloping solution a photosensitive resin film in a non-photoirradiatedportion that has not become insoluble in a developing solution. When thephotosensitive resin is a positive-type resin, a portion of thephotosensitive resin film which is not photoirradiated is insoluble in adeveloping solution and a portion of the photosensitive resin film thatis exposed by the photoirradiation becomes soluble in a developingsolution. Therefore, a development can be performed by dissolving andremoving with a developing solution a photosensitive resin film in aphotoirradiated portion which became soluble in a developing solution.

In the case of using a water-soluble photosensitive resin, a developingsolution used is, for example, water or the same developing solution asused in a general water-soluble photoresist. In the case of using anorganic solvent resin, a developing solution used may be an organicsolvent or the same developing solution as used in a solvent-typephotoresist. Here, as a step for forming a resin pattern, a forming stepusing a photosensitive resin has been described. In the case of using aresin other than the photosensitive resin, a resin pattern may be formedby lift-off or the like.

The absorbing step is a step for making the resin pattern formed asdescribed above absorb the above-described solution containing metalcomponents. The absorption can be performed by bringing the formed resinpattern into contact with the solution containing metal components. Morespecifically, the absorption can be performed, for example, by a dippingmethod in which the formed resin pattern is dipped in the solutioncontaining metal components or a coating method in which the solutioncontaining metal components is coated onto the formed resin pattern by amethod such as spray method or spin-coating method. Before contactingthe resin pattern with the solution containing metal components, forexample, in the case of using the above-described aqueous solution, theresin pattern may be swelled in advance using the above-describedaqueous solvent.

The washing step is a step performed after making the resinpattern-absorb the solution containing metal components, for removingand washing an excess solution adhering to the resin pattern or anexcess solution adhering to the parts other than the resin pattern. Thiswashing step can be performed using the same washing solution as thesolvent in the solution containing metal components, by a method ofdipping in this washing solution a substrate having formed thereon theresin pattern or by a method of spraying the washing solution onto asubstrate having formed thereon the resin pattern. The washing performedhere is not limited to a washing with a washing solution as long as theexcess solution can be washed away and thus it can be performed, forexample, by a method using air spraying or vibration. In this washingstep, the solution containing metal components may be slightly removed.However, the amount removed is extremely small and therefore, even ifthis is recovered and reused, can be drastically reduced as comparedwith the conventional method.

The burning step is a step for burning a resin pattern (a photosensitiveresin film in a photoirradiation portion in the case of a negative-typeresin and a photosensitive resin film in a non-photoirradiation portionin the case of a positive-type resin) that was obtained through thedeveloping step, the absorbing step and the washing step, anddecomposing and removing the organic components in the resin pattern toform an electrically conductive film using the metal components in thesolution containing metal components absorbed in the resin pattern. Theburning can be performed in an atmosphere when the electricallyconductive film to be formed is a noble metal film. Also, the burningcan be performed in a vacuum or a deoxidation atmosphere (for example,in an inert gas atmosphere such as nitrogen) when the electricallyconductive film to be formed is a film formed of a metal that easilyoxidize, such as copper and palladium. In the case of forming aninsulating pattern, an insulant can be formed by burning Pb or the likein an oxygen atmosphere (such as in an air). The burning can begenerally performed by placing the resin pattern under a temperature of400 to 600° C. for several minutes to several tens of minutes, thoughthe conditions vary according to the kinds of organic componentscontained in the resin pattern. The burning can be performed, forexample, by using a circulating hot air oven. By this burning, anelectrically conductive pattern can be formed on a substrate as a metalfilm having a shape according to the predetermined pattern.

After the burning step, a milling step may be performed if needed. Themilling step is a step of patterning a metal film formed on a substratesurface. The ion milling method used may be any of the generally usedmethods. The resist used may be a positive resist or a negative resist.In exposure, the photosensitive resin film is exposed using apredetermined mask and developed to obtain a predetermined pattern. Theexposed surface is etched by an ion milling method or the like. Theetching can be performed by any method as long as the metal surface canbe etched. Finally, the resist is peeled off, and the peeling solutionmay be selected as appropriate according to the kind of the resist used.

The preferable embodiment of the present invention was described above.According to this embodiment, a pattern can be formed with a highutilization efficiency of materials and at a low cost.

When forming a metal or metal compound pattern according to theabove-described preferable embodiment, it is important to control theabsorption ability of a resin pattern such as control of the resinpattern thickness, and to control the absorption conditions in theabsorbing step such as control of the dipping time or the coating time,for controlling the electrical properties of the formed pattern as wellas the function of preventing diffusion of dissimilar metals. By thiscontrol, the porosity of formed pattern can be desirably controlled.

Incidentally, the method for obtaining a pattern having a desiredporosity is not limited to the above-described manufacturing method, anda pattern having a desired porosity can also be obtained by the methodaccording to Examples 11 and 13 as described later.

Next, the porosity of the film pattern formed according to the presentinvention will be described in detail below.

(4) Porosity of Metal or Metal Compound Pattern

Diffusion Movement of Contamination Component and Stability of SheetResistance.

The film structure of the present invention, in which 60% or less ofporosity (40% or more of density) is provided, will be described.

Here, the porosity of a metal film pattern in the case of using it as anelectrode will be described. As described above, with regard to the filmquality of a metal film manufactured by sputtering method, the porosityis almost 0% (i.e., the density is 100%) and thus the density approachesthat of pure metal. By virtue of this, the metal film pattern is used asan electrode which is stable in electrode properties. It is found thatwhen this electrode is joined to dissimilar metals or contaminationmetal compounds, these dissimilar metals or contamination metalcompounds diffuse and move. For example, in a case where Ag of the likeis printed on a Pt electrode by sputtering method, a large amount of Agdiffuses on the Pt electrode. Accordingly, due to the diffusion ofdissimilar metals on the Pt electrode, the electrical properties of theelectrode change, which often becomes a problem.

It was verified that, when, in particular, Ag or the like diffuses to anelectrode constituting an electron emitting device, the diffusion ofdissimilar metals exerts great influence on electron emitting properties(Japanese Patent Application Laid-open No. 2000-243327). As a result ofour studies, it was proved that such diffusion of dissimilar metals canbe suppressed by providing voids on a metal or metal compound pattern.From the standpoint of preventing the diffusion of dissimilar metals, itis effective that the pattern preferably has the porosity of 10% ormore, more preferably 20% or more. In particular, when the diffusion ofdissimilar metals such as Ag to an electron emitting device takes place,the electron emitting property greatly changes depending on thediffusion amount, and therefore the diffusion amount of the dissimilarmetals must be suppressed to such a degree that does not cause anyadverse influence on electron emitting property. In order to attainthis, it was revealed that the porosity is preferably 10% or more, andmore preferably 20% or more.

On the other hand, when the porosity is 60% or more (density is 40% orless), the film becomes porous. In case of joining such an electrodewith dissimilar metals, contamination metal compounds or the like, itwas found that, since a movement path of the dissimilar metal to bediffused is porous, an environment where it is difficult for thedissimilar metal to move is formed. However, such a porous electrodehaving the porosity of 60% or more is inferior in the resistancestability, and therefore there is a case where the porous electrode maynot obtain stable properties. This also gives rise to a problem not onlyin an electrically conductive pattern such as an electrode but also inan insulating pattern because the electrical properties (insulatingproperty) are insufficient.

During the formation of an electrode on a large substrate such as PDP,the film thickness distribution may vary on the order of ±20% in such aporous electrode. In such a case, the variation of the resistance valueis greater than that of the film thickness distribution, which is aproblem as a device using the electrode.

In view of this, in the metal or metal compound pattern of the presentinvention, the variation of sheet resistance can be minimized andmoreover, there arises no problem in electrode properties. Further, inthe case of using the pattern as the electrode of the electron emittingdevice, the diffusion movement of dissimilar metals or contaminationmetal compounds can be suppressed and the degradation of electronemitting property can be suppressed.

Calculation Method of Porosity

The porosity as described in the present invention is calculated basedon the measured value of density. First, the calculation method ofdensity is described Pt electrode as an example. The density is providedas the Pt abundance per unit volume.

Pt density=(Pt abundance of the present invention/film thickness)/(Ptabundance of reference/film thickness)

Where, the Pt abundance of reference is a Pt abundance of Pt patternformed by a sputtering process. Pt abundance was measured using EPMA(electron probe·microanalyzer).

On the basis of the thus obtained density, the porosity is provided as:Pt porosity=1−Pt density. The film thickness was measured using a stylussystem thicknessmeter.

(5) Manufacturing Method of Electron Emitting Device, Electron Sourceand Image-Forming Apparatus

The above-described electrically conductive pattern formation method ofthe present invention may be suitably applied to a manufacturing methodof: an electron emitting device comprising electrodes; an electronsource providing a plurality of electron emitting devices havingelectrodes and a wiring for driving the plurality of electron emittingdevices; and further an image-forming apparatus comprising this electronsource and an image-forming member for forming an image by theirradiation of electron beam emitted from an electron emitting device ofthe electron source. More specifically, for the manufacture of theelectron emitting device, an electrode is formed according to the methodof the present invention; and for the manufacture of the electron sourceor the image-forming apparatus, one or both of the electrodes of theelectron emitting device and the wiring used is (are) formed accordingto the method of the present invention, whereby the amount of materialsconstituting the electrode and/or the wiring which are removed duringthe manufacturing step can be greatly reduced and the time and laborrequired for processing such materials removed during the manufacturecan be greatly reduced.

As described hereinabove, preferred examples of the electron emittingdevice having the electrodes that are manufactured using theelectrically conductive pattern forming method of the present inventionpreferably includes a cold cathode device such as a surfaceconductive-type electron emitting device, a field emission-type(FE-type) electron emitting device and a metal/insulatinglayer/metal-type (MIM-type) electron emitting device. Among these,particularly preferred is a surface conductive-type electron emittingdevice in which a large number of electrodes of electron emittingdevices can be easily formed at one processing using the method of thepresent invention. According to the method of the present invention,simultaneous with formation of the device electrodes for the pluralityof electron emitting devices, a wiring necessary for driving eachelectron emitting device can be formed. Therefore, the electron sourcehaving a plurality of the electron emitting devices can be easilymanufactured and further, the manufacture of an image-forming apparatus,which is achieved by combining this electron source with animage-forming member for forming an image by the irradiation of anelectron beam from the electron emitting device constituting theelectron source, can be made significantly easier.

Examples

The present invention is described in greater detail below by referringto the Examples, however, the present invention is not limited to theseexamples.

Example 1

A solution obtained by adding 0.06 wt % of an amine silane couplingagent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd.) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a roll coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, using anegative photomask, the substrate and the mask were brought into contactwith each other, and an exposure was performed thereon for 2 seconds inexposing time by an ultra-high pressure mercury lamp 2 (illuminance: 8.0mW/cm²) as a light source. Thereafter, the resulting substrate wasprocessed by dipping for 30 seconds in pure water as a developer, thusobtaining an objective resin pattern. The film thickness of the resinpattern obtained was 1.55 μm.

This resin pattern-formed substrate was dipped in pure water for 30seconds and, then, dipped in a Pt—Pb solution (platinum (II)monoethanolamine acetate complex·platinum content: 2% by weight/lead(II) acetate·lead content: 200 ppm) for 60 seconds.

Subsequently, the substrate was taken out from the Pt—Pb solution,washed with flowing water for 5 seconds to wash the Pt complex solutionbetween the resin patterns, dewatered by spraying thereon air and driedfor 3 minutes by a hot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having adistance between electrodes of 20 μm, a width of 60 μm, a length of 120μm and a thickness of 20 nm.

The sheet resistance of this electrode was 60 Ω/□.

Example 2

A platinum electrode was formed in the same manner as in Example 1except for using a Pt solution (tetraammineplatinum (II) acetate complexplatinum content: 2% by weight) as a metal organic compound solution.

The thickness of this electrode was 25 nm and the sheet resistancethereof was 40 Ω/□.

Example 3

A platinum electrode was formed in the same manner as in Example 1except for using a Pt—Pb solution (tetraammineplatinum (II) acetatecomplex·platinum content: 2% by weight/lead (II) acetate·lead content:200 ppm) as a metal organic compound solution.

The thickness of this electrode was 30 nm and the sheet resistancethereof was 55 Ω/□.

Example 4

Using the electrically conductive pattern forming method of the presentinvention, a plurality of surface conductive-type electron emittingdevices were manufactured and, moreover, a wiring for driving thisplurality of surface conductive-type electron emitting devices wasformed to thereby manufacture an electron source. Further, animage-forming apparatus was manufactured using this electron source. Themanufacturing procedure thereof will be described below on the basis ofFIG. 1 and FIG. 2.

Step 1: On a glass-made substrate 1 having a size of 300 mm inlength×300 mm in width×2.8 mm in thickness, a plurality of deviceelectrode pairs (first region) as shown in FIG. 1 were manufactured inthe same manner as in Example 1.

The device electrode pair in this Example was formed by opposing adevice electrode A having a width of 60 μm and a length of 480 μm to adevice electrode B having a width of 120 μm and a length of 200 μm in anelectrode gap of 20 μm. The device electrode pairs were disposed on thesubstrate 1 in a matrix form by adjusting so that the pitch between thedevice electrode pair was 300 μm in a lateral direction and 650 μm in alongitudinal direction and the number of device electrode pairs was720×240. A platinum film pattern having a size of 1 cm×1 cm was formedat the same time as the formation of the device electrode pair. Thesheet resistance in that case was measured and it was found to be 26Ω/□.

Step 2: As shown in FIG. 2, an X direction wiring 2 (second region)connecting one device electrode A of the device electrode pair in eachline was provided using an Ag paste by a screen printing method.Subsequently, an interlayer insulating layer (not shown in the figure)having a thickness of 20 μm was provided by a screen printing method,and a Y-direction wiring 3 (second region) connecting another deviceelectrode B of the device electrode pair in each line was providedthereon in the same manner as in the X-direction wiring 2 and thesubstrate was burned. In this manner, the X-direction wiring 2 and theY-direction wiring 3 were provided.

Step 3: The substrate 1 having formed thereon the X-direction wiring 2and the Y-direction wiring 3 in Step 2 was washed with pure water.

Step 4: In an aqueous solution having dissolved therein polyvinylalcohol in a concentration of 0.05% by weight, 2-propanol in aconcentration of 15% by weight and ethylene glycol in a concentration of1% by weight, a palladium-monoethanolamine acetate complex was dissolvedso as to have a palladium concentration of about 0.15% by weight,whereby a light yellow aqueous solution was obtained.

By an ink jet method, droplets of the above-described aqueous solutionwere imparted four times to the same portion from the upper position ofthe device electrodes A and B constituting each device electrode pair soas to straddle the device electrodes A and B and to be given within theelectrode gap (dot size=about 100 μm).

The substrate 1 having given thereon the droplets of the aqueoussolution was burned for 30 minutes in a burning oven at 350° C., apalladium thin film 4 for connecting between the device electrodes A andB constituting the device electrode pair was formed between each deviceelectrode pair, and then the substrate 1 was fixed on a rear plate 5.

Step 5: A face plate 10, in which a fluorescent film 8 and a metal back9 were formed on the inner surface of a glass-made substrate 7 that isdifferent from the substrate 1, was caused to face the rear plate 5, andthese were sealed through a supporting frame 6 to thereby constitute anenvelope 11. To the supporting frame 6, an air supply and exhaust pipeused for ventilating and exhausting air was adhered in advance.

Step 6: After exhausting the inside of the envelope to 1.3×10⁻⁵ Pathrough the air supply and exhaust pipe, a forming was performed inevery line in a manner that, by using X-direction terminals D_(x1) toD_(xn) ranging with each X-direction wiring 2 and the Y-directionterminals D_(y1) to D_(ym) ranging with each Y-direction wiring 3, avoltage was applied between the device electrode pairs in each line toproduce a cracking part having a size of tens of μm on the palladiumthin film 4 between the device electrodes A and B, whereby a surfaceconductive-type electron emitting device was formed.

Step 7: After exhausting the inside of the envelope 11 to 1.3×10⁻⁵ Pa,benzonitrile was introduced into the envelope 11 from the air supply andexhaust pipe until the inside of the envelope 11 is elevated to 1.3×10⁻²Pa. In the same manner as in the above-described forming, a pulsevoltage was fed between each device electrode pair and an activation fordepositing a carbon on the cracking portion of the palladium thin filmwas performed. The pulse voltage was applied for 25 minutes to eachline.

Step 8: The inside of the envelope 11 was sufficiently exhausted throughthe air supply and exhaust pipe and, then, further exhausted whileheating the entire envelope 11 at 250° C. for 3 hours. Finally, a getterwas flashed thereto and the air supply and exhaust pipe was sealed.

In this manner, a display panel as shown in FIG. 2 was manufactured, anda driving circuit comprising a scan circuit, a control circuit, amodulation circuit and a d.c. voltage source (all are not shown) wasconnected thereto, thereby manufacturing a panel-shaped image-formingapparatus.

A predetermined voltage was applied by time sharing to each surfaceconductive-type electron emitting device through the X-directionterminals D_(x1) to D_(xn) and the Y-direction terminals D_(Y1) toD_(Ym), and a high voltage was applied to the metal back 9 through thehigh voltage terminal 12, whereby an arbitrary matrix image pattern canbe displayed with a preferable image quality. Note that, when the panelwas decomposed and the diffusion of Ag to the electron emitting devicewas measured, it was confirmed that the diffusion of Ag was sufficientlyprevented.

In this Example, the manufacturing method of Example 1 was applied toform the device electrode. However, in the constitution in which thewiring electrode in contact with other metal, provided that themanufacturing method of Example 1 was applied to the formation of thewiring, the same effects as the above can be obtained.

Example 5

An image-forming apparatus was manufactured in the same manner as inExample 4 except for using a Pt—Pb solution (tetraammineplatinum (II)acetate complex·platinum content: 2% by weight/lead (II) acetate·leadcontent: 200 ppm) as a metal organic compound solution. An arbitrarymatrix image pattern was able to be displayed with a preferable imagequality.

Example 6

A solution obtained by adding 0.06 wt % of an amine silane couplingagent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd.) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a spin coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, using anegative photomask, the substrate and the mask were brought into contactwith each other, and an exposure was performed thereon for 2 seconds inexposing time by an ultra-high pressure mercury lamp (illuminance: 8.0mW/cm²) as a light source Thereafter, the resulting substrate wasprocessed by dipping for 30 seconds in pure water as a developer, thusobtaining an objective pattern. The film thickness of the pattern formedwas 0.98 μm.

This substrate was dipped in pure water for 30 seconds and, then, dippedin a Pt complex solution (platinum (II) monoethanolamine acetatecomplex·platinum content: 2% by weight) for 30 seconds.

Subsequently, the substrate was taken out from the Pt complex solution,washed with a flowing water for 5 seconds to wash the Pt complexsolution between the patterns, dewatered with air and dried for 3minutes by a hot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having athickness of 30 nm.

The sheet resistance of this electrode was 80 Ω/□.

Example 7

A solution obtained by adding 0.06 wt % of an amine silane couplingagent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a spin coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, using anegative photomask, the substrate and the mask were brought into contactwith each other, and an exposure was performed thereon for 2 seconds inthe exposing time by an ultra-high pressure mercury lamp (illuminance:8.0 mW/cm²) as a light source. Thereafter, the resulting substrate wasprocessed by dipping for 30 seconds in pure water as a developer, thusobtaining an objective pattern. The film thickness of the pattern formedwas 1.08 μm.

This pattern formed-substrate was dipped in pure water for 30 secondsand, then, dipped in a Pt—Pb solution (platinum (II) monomethanolamineacetate complex·platinum content: 2% by weight/lead (II) acetate·leadcontent: 200 ppm) for 30 seconds.

Subsequently, the substrate was taken out from the Pt—Pb solution,washed with flowing water for 5 seconds to wash the Pt—Pb solutionbetween the patterns, dewatered with air and dried for 3 minutes by ahot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having adistance between electrodes of 20 μm, a width of 60 μm, a length of 120μm and a thickness of 40 nm.

The sheet resistance of this electrode was 120 Ω/□.

Examples 7-2

A platinum electrode was formed in the same manner as in Example 7except for changing the metal organic compound solution to a Pt—Rusolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/ruthenium (III) chloride·ruthenium content: 200ppm) and changing the dipping time to 120 seconds. A platinum electrodehaving a distance between electrodes of 20 μm, a width of 60 μm, alength of 120 μm and a thickness of 42 nm was formed. The sheetresistance of this electrode was 12 Ω/□.

Examples 7-3

A platinum electrode was formed in the same manner as in Example 7except for changing the metal organic compound solution to a Pt—Snsolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/stannum (III) chloride·stannum content: 200 ppm)and changing the dipping time to 30 seconds. A platinum electrode havinga distance between electrodes of 20 μm, a width of 60 μm, a length of120 μm and a thickness of 56 nm was formed. The sheet resistance of thiselectrode was 80 Ω/□.

Examples 7-4

A platinum electrode was formed in the same manner as in Example 7except for changing the metal organic compound solution to a Pt—Vsolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/vanadyl (IV) salfate·vanadium content: 200 ppm)and changing the dipping time to 60 seconds. A platinum electrode havinga distance between electrodes of 20 μm, a width of 60 μm, a length of120 μm and a thickness of 38 nm was formed. The sheet resistance of thiselectrode was 64 Ω/□.

Example 8

A resin (polyvinyl alcohol) was coated over the entire surface of aglass substrate (75 mm in length×75 mm in width×2.8 mm in thickness)with a spin coater and dried at 45° C. for 2 minutes using a hot plate.Subsequently, the entire surface of the substrate was exposed for 2seconds in exposing time by an ultra-high pressure mercury lamp(illuminance: 8.0 mW/cm²) as a light source. Thereafter, the resultingsubstrate was processed by dipping for 30 seconds in pure water as adeveloper. The film thickness thereof was 1.85 μm.

This substrate was dipped in pure water for 30 seconds and, then, dippedin a Pt—Pb solution (platinum (II) monoethanolamine acetatecomplex·platinum content: 2% by weight/lead (II) acetate·lead content:200 ppm) for 120 seconds.

Subsequently, the substrate was taken out from the Pt—Pb solution,washed with a flowing water for 5 seconds to wash the Pt—Pb solutionbetween the patterns, dewatered with air and dried for 3 minutes by ahot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having adistance between electrodes of 20 μm, a width of 60 μm, a length of 120μm and a thickness of 60 nm.

The sheet resistance of this electrode was 160 Ω/□.

Subsequently, a resist (positive-type resist LC100/10cp, produced byShipley Company) was coated (1200 rpm/5 seconds, film thickness: 1.3micron) on this substrate with a spinner.

The coated resist was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to form an objective pattern and aplatinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm and a length of 120 μm.

Example 8-2

A platinum electrode was formed in the same manner as in Example 8except for changing the metal organic compound solution to a Pt—Znsolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/zinc (II) acetate·zinc content: 200 ppm) andchanging the dipping time to 15 seconds.

A platinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm, a length of 120 μm and a thickness of 44 nm was formed.The sheet resistance of this electrode was 250 Ω/□.

Example 8-3

A platinum electrode was formed in the same manner as in Example 8except for changing the metal organic compound solution to Pt—Rhsolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/rhodium (III) nitrate·rhodium content: 200 ppm)and changing the dipping time to 60 seconds.

A platinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm, a length of 120 μm and a thickness of 51 nm was formed.The sheet resistance of this electrode was 190 Ω/□.

Example 8-4

A platinum electrode was formed in the same manner as in Example 8except for changing the metal organic compound solution to a Pt—Crsolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/chromium (III) acetate·chromium content: 200 ppm)and changing the dipping time to 60 seconds.

A platinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm, a length of 120 μm and a thickness of 43 nm was formed.The sheet resistance of this electrode was 99 Ω/□.

Example 9

A resin (polyvinyl alcohol) was coated over the entire surface of aglass substrate (75 mm in length×75 mm in width×2.8 mm in thickness)with a spin coater and dried at 45° C. for 2 minutes using a hot plate.Subsequently, the entire surface of the substrate was exposed for 2seconds in exposing time by an ultra-high pressure mercury lamp(illuminance: 8.0 mW/cm²) as a light source. Thereafter, the resultingsubstrate was processed by dipping for 30 seconds in pure water as adeveloper. The film thickness thereof was 2.3 μm.

This substrate was dipped in pure water for 30 seconds and, then, dippedin a Pt—Pb solution (platinum (II) monoethanolamine acetate complexplatinum content: 2% by weight/lead (II) acetate lead content: 200 ppm)for 60 seconds.

Subsequently, the substrate was taken out from the Pt—Pb solution,washed with flowing water for 5 seconds to wash the Pt—Pb solutionbetween the patterns, dewatered with air and dried for 3 minutes by ahot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having adistance between electrodes of 20 μm, a width of 60 μm, a length of 120μm and a thickness of 60 nm.

The sheet resistance of this electrode was 39 Ω/□.

Subsequently, a resist (positive-type resist LC100/10cp, produced byShipley Company) was coated (1200 rpm/5 seconds, film thickness: 1.3micron) on this substrate with a spinner.

The coated resist was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to form an objective pattern and aplatinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm and a length of 120 μm.

Example 9-1

A platinum electrode was formed in the same manner as in Example 9except for changing the metal organic compound solution to a Pt—Bisolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/EDTANH4-bismuth (III) acetate·bismuth content: 200ppm) and changing the dipping time to 90 seconds.

A platinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm, a length of 120 μm and a thickness of 32 nm was formed.The sheet resistance of this electrode was 66 Ω/□.

Example 9-2

A platinum electrode was formed in the same manner as in Example 9except for changing the metal organic compound solution to a Pt—Sisolution (platinum (II) monoethanolamine acetate complex·platinumcontent: 2% by weight/3-(2-aminoethyl)propyltriethoxysilane·siliconcontent: 200 ppm) and changing the dipping time to 60 seconds.

A platinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm, a length of 120 μm and a thickness of 78 nm was formed.The sheet resistance of this electrode was 105 Ω/□.

Example 10

A resin (polyvinyl alcohol) was coated over the entire surface of aglass substrate (75 mm in length×75 mm in width×2.8 mm in thickness)with a spin coater and dried at 45° C. for 2 minutes using a hot plate.Subsequently, the entire surface of the substrate was exposed for 2seconds in exposing time by an ultra-high pressure mercury lamp(illuminance: 8.0 mW/cm²) as a light source. Thereafter, the resultingsubstrate was processed by dipping for 30 seconds in pure water as adeveloper. The film thickness thereof was 2.3 μm.

This substrate was dipped in pure water for 30 seconds and then, dippedin a Pt solution (platinum (II) monoethanolamine acetate complexplatinum content: 2% by weight) for 120 seconds.

Subsequently, the substrate was taken out from the Pt solution, washedwith a flowing water for 5 seconds to wash the Pt complex solutionbetween the resin patterns, dewatered with air and dried for 3 minutesby a hot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having adistance between electrodes of 20 μm, a width of 60 μm, a length of 120μm and a thickness of 40 nm.

The sheet resistance of this electrode was 18 Ω/□.

Subsequently, a resist (positive-type resist LC100/10cp, produced byShipley Company) was coated (1200 rpm/5 seconds, film thickness: 1.3micron) on this substrate with a spinner.

The coated resist was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by ion milling method, andthen the resist was peeled off using a resist peeling solution (1112A,produced by Shipley Company) to form an objective pattern and a platinumelectrode having a distance between electrodes of 20 μm, a width of 60μm and a length of 120 μm.

Example 11

A metal organic compound aqueous solutiontetrakis(monoethanolamino)platinum (II) acetate complex·platinumcontent: 5% by weight and a resin (polyvinyl alcohol) aqueous solutionwere mixed in the following ratio to thereby prepare a composition 11-A.

Metal organic compound: 50 parts by weight

Polyvinyl alcohol resin: 50 parts by weight

This composition 11-A was coated over the entire surface of a glass-madesubstrate (75 mm in length×75 mm in width×2.8 mm in thickness) with aspin coater and dried at 80° C. for 2 minutes. The film thickness afterdrying was 2.1 μm.

Subsequently, the substrate having coated film was placed in acirculating hot air oven and burned at 500° C. for 30 minutes. As aresult, a platinum having a thickness of 60 nm was formed. Using asimultaneously-formed platinum film pattern having a size of 1 cm×1 cm,the sheet resistance was measured, and it was found to be 14 Ω/□.

Thereafter, on this substrate, a resist (positive-type resistLC100/10cp, produced by Shipley Company) was coated (1200 rpm/5 seconds,film thickness: 1.3 micron) with a spinner.

The coated resist was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to form an objective pattern and aplatinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm and a length of 120 μm.

Example 12

A solution obtained by adding 0.06 wt % of an amine silane couplingagent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd.) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a spin coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, the substrateand the mask were brought into contact with each other, and the entiresurface of the substrate was exposed for 2 seconds in exposing time byan ultra-high pressure mercury lamp (illuminance: 8.0 mW/cm²) as a lightsource. Thereafter, the resulting substrate was processed by dipping for30 seconds in pure water as a developer, thus obtaining an objectivepattern. The film thickness thereof after the pattern formation was 1.55μm.

This substrate was dipped in a Pt complex solution (platinum (II)monoethanolamine acetate complex·platinum content: 2% by weight) for 120seconds.

Subsequently, the substrate was taken out from the Pt complex solution,washed with flowing water for 5 seconds to wash the Pt complex solutionbetween the patterns, dewatered with air and dried for 3 minutes by ahot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having athickness of 76 nm.

The sheet resistance of this electrode was 9 Ω/□.

Thereafter, on this substrate, a resist (positive-type resistLC100/10cp, produced by Shipley Company) was coated (1200 rpm/5 seconds,film thickness: 1.3 micron) with a spinner.

The coated resist was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to form an objective pattern and aplatinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm and a length of 120 μm.

Example 13

A metal organic compound bis(acetylacetonato)platinum (II) and anacrylic copolymer resin propylene glycol monomethyl ether solution weremixed in the following ratio to prepare a composition 13-A.

Metal organic compound: 50 parts by weight

Acrylic copolymer resin: 50 parts by weight

This composition 13-A was coated over the entire surface of a glass-madesubstrate (75 mm in length×75 mm in width×2.8 mm in thickness) with aspin coater and dried at 80° C. for 2 minutes by a hot plate. The filmthickness thereof after drying was 1.5 μm.

Subsequently, the substrate having the coated film was placed in acirculating hot air oven and burned at 550° C. for one hour. As aresult, a platinum having a thickness of 42 nm was formed. The sheetresistance of this platinum was measured, and it was found to be 35 Ω/□.

Thereafter, on this substrate, a resist (positive-type resistLC100/10cp, produced by Shipley Company) was coated (1200 rpm/5 seconds,film thickness: 1.3 micron) with a spinner.

The coated resin was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to form an objective pattern and aplatinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm and a length of 120 μm.

Example 14

A cyclized rubber and a 4,4′-diazidochalcone xylene solution were mixedin the following ratio to prepare a composition 14-A.

Cyclized rubber: 95 parts by weight

4,4′-diazidochalcone: 5 parts by weight

This composition 14-A was coated over the entire surface of a glass-madesubstrate (75 mm in length×75 mm in width×2.8 mm in thickness) with aspin coater and dried at 80° C. for 2 minutes using a hot plate. Thefilm thickness thereof after drying was 1.5 μm.

Subsequently, using a negative photomask, the substrate and the maskwere brought into contact with each other, and an exposure was performedthereon for 10 seconds in exposing time by an ultra-high pressuremercury lamp (illuminance: 8.0 mW/cm²) as a light source. Thereafter,the resulting substrate was processed by dipping for 30 seconds inxylene as a developer to obtain an objective resin pattern. The filmthickness thereof after the pattern formation was 1.0 μm.

This substrate was dipped in a Pt complex acetone solution(bis(acetylacetonato)platinum (II) platinum content: 2% by weight) for30 seconds.

Subsequently, the substrate was taken out from the Pt complex acetonesolution, washed with flowing water for 5 seconds to wash the Pt complexsolution between the patterns, dewatered with air and dried for 3minutes by a hot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having athickness of 25 nm.

The sheet resistance of this electrode was 100

Comparative Example

On a glass-made substrate (75 mm in length×75 mm in width×2.8 mm inthickness), Ti was first deposited at a thickness of 5 nm and Pt wassubsequently deposited at a thickness of 45 nm by sputtering method.Subsequently, on this substrate, a resist (positive-type resist LC100/10cp, produced by Shipley Company was coated (1200 rpm/5 seconds, filmthickness: 1.3 μm) with a spinner.

The coated film was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to obtain an objective pattern.Using a simultaneously-formed platinum film pattern having a size of 1cm×1 cm, the sheet resistance was measured, and it was found to be 5.5Ω/□.

Using EPMA (electron probe·microanalyzer), the substrate manufacturedabove was subjected to measurement of the Pt amount on the substrate.

The results thereof are shown in Table 1.

TABLE 1 Sheet Film resistance thickness No. (Ω/□) (nm) EPMA PorosityDensity Remark Density Comparative 5.5 45 2500 0.00 1.00 Litho refexample 1 60 20 500 0.55 0.45 Pt—Pb Dense 2 40 25 580 0.58 0.42 Pt Dense3 55 30 770 0.54 0.46 Pt—Pb Dense 6 80 30 400 0.76 0.24 Pt Non-dense 7120 40 700 0.69 0.32 Pt—Pb Non-dense 7-2 12 42 820 0.65 0.35 Pt—RuNon-dense 7-3 80 56 650 0.79 0.21 Pt—Sn Non-dense 7-4 64 38 700 0.670.33 Pt—V Non-dense 8 160 60 800 0.76 0.24 Pt—Pb Non-dense 8-2 250 44420 0.83 0.17 Pt—Zn Non-dense 8-3 190 51 800 0.72 0.28 Pt—Rh Non-dense8-4 99 43 750 0.69 0.31 Pt—Cr Non-dense 9 39 60 2000 0.40 0.60 Pt—PbDense 9-2 66 32 1450 0.18 0.82 Pt—Bi Dense 9-3 108 78 3500 0.19 0.81Pt—Si Dense 10 20 40 1500 0.33 0.68 Pt Dense 11 14 60 2600 0.22 0.78 PtDense 12 9 76 2900 0.31 0.69 Pt Dense 13 35 42 1250 0.46 0.54 Pt Dense14 100 25 350 0.75 0.25 Pt Non-dense

Further, masking was performed on a part of the electrodes of thesubstrate manufactured in Comparative Example and the above-describedsome Examples, and Ag was deposited thereon at a thickness of 500 nm bysputtering.

This substrate was burned at 400° C. for 1 hour in a circulating hot airoven.

Using EPMA, this substrate was measured on the Ag value at a position of500 μm from the edge portion generated by sputtering Ag on the Ptelectrode.

The results thereof are shown in Table 2.

TABLE 2 Judgment of Resistance manufacturing Overall No. Porosity AgDiffusion Stability Cost Judgement Comparative 0 1000 X ◯ X X exampleExample 1 0.55 200 ◯ ◯ ◯ ⊚ Example 2 0.58 180 ◯ ◯ ◯ ⊚ Example 6 0.76 110◯ X ◯ Δ Example 7 0.69 140 ◯ X ◯ Δ Example 8 0.76 140 ◯ X ◯ Δ Example 90.40 250 ◯ ◯ ◯ ⊚ Example 9-2 0.18 490 Δ ◯ ◯ ◯ Example 10 0.33 320 ◯ ◯ ◯⊚ Example 11 0.22 400 ◯ ◯ ◯ ⊚ Example 13 0.46 240 ◯ ◯ ◯ ⊚ Note: ⊚indicates Excellent, ◯ indicates Good, Δ_(.) indicates Available, and Xindicates Inferior

Example 15

Using the same method as in Example 4, a plurality of surfaceconductive-type electron emitting devices were manufactured and, at thesame time, a wiring for driving this plurality of surfaceconductive-type electron-emitting devices was formed to therebymanufacture an electron source and moreover, an image-forming apparatuswas manufactured using this electron source. Here, a pair of deviceelectrodes was prepared so as to have a shape that the distance from thecontact portion of the device electrodes with the wiring to anelectron-emitting portion was 500 μm.

Note that, a pair of device electrodes was manufactured using thefollowing Examples and Comparative Examples of the present invention.Comparative Examples 2 and 3 are examples in which the film thickness ofthe resin pattern and the dipping time of the resin pattern to a metalsolution in Example 9-2 were desirably controlled and a pattern having adifferent porosity is obtained, for comparing the relation between theporosity and the electron emitting properties.

In this way, a display panel as shown in FIG. 2 was manufactured, andthen a drive circuit comprising a scan circuit, a control circuit, amodulation circuit, a d.c. voltage source and the like (all are notshown) was connected thereto to manufacture a panel-form image-formingapparatus.

A predetermined voltage was applied by time sharing to each surfaceconductive-type electron emitting device through the X-directionterminals D_(X1) to D_(Xn) and the Y-direction terminals D_(Y1) toD_(Ym), and a high voltage was applied to the metal back 9 through thehigh voltage terminal 12, whereby an image pattern was displayed.

The results thereof were shown in Table 3.

TABLE 3 Comparison of Electron-Emitting No. Porosity Ag PropertiesComparative 0 1000 0.5 example Comparative 0.08 800 0.76 example 2Comparative 0.1 750 0.83 example 3 Example 1 0.55 200 1 Example 2 0.58180 0.98 Example 6 0.76 110 0.99 Example 7 0.69 140 1 Example 8 0.76 1401 Example 9 0.40 250 0.98 Example 9-2 0.18 490 0.87 Example 10 0.33 3200.98 Example 11 0.22 400 0.93 Example 13 0.46 240 1

As described above, in order to obtain a preferable electron emittingproperty in the relation between the electron emitting properties andthe porosity, it can be said that the porosity is preferably 10% ormore, more preferably 20% or more. Taking account of the above-describedstability of the resistance, it is preferable to satisfy the porosity of60% or less. Also, as an electrode pattern, it can be said that, in viewof Ag diffusion, the porosity is preferably 10% or more, more preferably20% or more, and in view of the resistance stability, the porosity ispreferably 60% or less.

Example 16

In this Example and Example 17, a resin pattern was formed using a resinhaving an ion exchange function. More specifically, a resin having acarboxylic acid group was used. As a result, the absorption of metalmaterials was more improved, and a manufacturing method at a low cost inwhich the use efficiency of materials is enhanced can be provided.Example 16 will be described in detail below. In this Example, aphotosensitive resin containing polymer components (methacrylicacid-methylmethacrylicacid-ethylacrylate-n-butylacrylate-azobisisobutyronitrile copolymer) asdescribed in Patent Registration NO. 02527271 was coated over the entiresurface of a glass substrate (75 mm in length×75 mm in width×2.8 mm inthickness) with a roll coater and dried at 45° C. for 2 minutes using ahot plate. Subsequently, using a negative photomask, the substrate andthe mask were contacted with each other, and an exposure was performedthereon for 2 seconds in exposing time by an extra-high pressure mercurylamp (illuminance: 8.0 mW/cm²) as a light source. Thereafter, theresulting substrate was processed by dipping for 30 seconds in purewater as a developing solution to obtain an objective resin pattern. Thefilm thickness of the resin pattern obtained was 1.35 μm.

This resin pattern-formed substrate was dipped in pure water for 30seconds and then dipped in a Pt—Pb solution (platinum (II)monoethanolamine acetate complex:platinum content: 2% by weight/lead(II) acetate:lead content: 200 ppm)) for 60 seconds.

Subsequently, the substrate was taken out from the Pt—Pb solution,washed with a flowing water for 5 seconds to wash the Pt complexsolution between the resin patterns, dewatered by spraying thereon airand dried for 3 minutes by a hot plate at 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having adistance between electrodes of 20 μm, a width of 60 μm, a length of 120μm and a thickness of 15 nm.

The sheet resistance of this electrode was 80 Ω/□.

Example 17

Using the resin pattern manufactured in Example 16, instead of dippingit in the Pt—Pb solution, the solution was imparted two times on theresin pattern by an ink jet apparatus (Bubble Jet Printer Head BC-01,manufactured by Canon Co., Inc.) and dried for 3 minutes by a hot plateat 80° C.

Thereafter, the substrate dried was burned at 500° C. for 30 minutes ina circulating hot air oven to form a platinum electrode having adistance between electrodes of 20 μm, a width of 60 μm, a length of 120μm and a thickness of 15 nm. In case of this Example, the washing stepis not required, and therefore the number of steps can be reduced.

Also, the sheet resistance of this electrode was 85 Ω/□.

In Examples 16 and 17 above, also, a pattern was able to be formed witha good use efficiency of materials. Further, the electrode patternsmanufactured according to the methods of Examples 16 and 17 above areused for the device electrode of the image-forming apparatus in Example4. As a result, preferable electron emitting properties was able to beobtained and a preferable image display was able to be realized.

The present invention is as described above, and exhibits the followingeffects.

(1) The materials constituting a pattern are scarcely removed in thecourse of the process for forming the metal or the metal compoundpattern, and therefore, for example, at the formation of an electricallyconductive pattern such as an electrode or a wiring, electricallyconductive pattern constituting materials that are to be removed duringthe process can be suppressed to the minimum, and even when theelectrically conductive pattern is constituted by a noble metal such asplatinum, a load bearing at the time of recovering and reusing theelectrically conductive pattern constituting materials that are to beremoved during the process can be reduced to the minimum. Further, if anelectron emitting device, an electron source and an image-formingapparatus are manufactured using this method of forming the electricallyconductive pattern, the above-described load at the time ofmanufacturing those can be greatly reduced.

(2) From the same reason as that described above, since a pattern can beformed using the minimum required amount of metal component, the costrequired at the time of forming a large number of electrodes, wiringpatterns or insulating layers over a large area can be suppressed.

(3) In the present invention, a water-soluble photosensitive resin isused as a photosensitive resin and a solution containing metalcomponents is prepared as an aqueous solution, whereby an adverseinfluence exerted on the natural environment in addition to a workingenvironment can be suppressed to the minimum and, at the same time, apatterning does not require the use of a strong acid, with the resultthat there is no fear that the precision decreases due to the corrosionof the substrate due to a strong acid, and a desired fine electricallyconductive pattern can be formed without lowering the precision.

(4) In particular, by selecting such a metal organic compound (a metalcomplex having a specified ligand) that a crystal is hardly precipitatedin the drying step, a metal film formed as an electrically conductivepattern can be rendered an uniform with good quality.

Further, an embodiment mode in which the porosity is controlled exhibitsthe following effects.

(5) If a film quality of a metal or a metal compound pattern iscontrolled, the use ratio of materials is reduced while maintaining theelectrical properties as a pattern, such as the resistance in the caseof using it as an electrode or the insulating property in the case ofusing it as an insulating layer, as a result, whereby the cost can bereduced.

(6) The diffusion and movement of the dissimilar metal can be greatlysuppressed in the presence of dissimilar metal.

(7) In particular, when the pattern is used for an electrodeconstituting an electron emitting device, the deterioration of electronemitting properties due to diffusion of dissimilar metals can beprevented and a preferable image-forming apparatus can be provided.

1.-15. (canceled)
 16. A method of manufacturing a metal or a metalcompound pattern, comprising: a coating step of coating a photosensitiveresin of negative-type on a surface of a substrate, the resin havingwater soluble characteristics; an exposing step of exposing the coatedphotosensitive resin to a light with a mask; a removing step of removinga light-unexposed portion of the coated photosensitive resin andmaintaining a light-exposed portion which forms a resin patterncorresponding to the metal or metal compound pattern by developing thephotosensitive resin subjected to the exposing step with a developingwater solution; subsequent to the removing step, an absorbing step ofmaking the resin pattern absorb a water solution containing metalcomponents; and a burning step of burning the resin pattern that hasabsorbed the solution containing metal components, to remove a resincomponent therefrom and maintain the patterned metal components whichbecome the metal or metal compound pattern thereon, wherein performanceof said absorbing step makes the resin pattern absorb an amount of thewater solution containing metal components sufficient to form the metalor metal compound pattern to have a thickness of 15 nm to 78 nm.
 17. Themethod of manufacturing a metal or metal compound pattern according toclaim 1, further comprising a washing step of washing the substratehaving formed thereon the resin pattern that has absorbed the solutioncontaining metal components, the washing step being conducted after theabsorbing step and before the burning step.
 18. The method ofmanufacturing a metal or metal compound pattern according to claim 1,wherein the resin has a carboxylic acid group.
 19. The method ofmanufacturing a metal or metal compound pattern according to claim 1,wherein the solution containing metal components is an aqueous solutionobtained by dissolving a water-soluble metal organic compound in anaqueous solvent component.
 20. The method of manufacturing a metal ormetal compound pattern according to claim 19, wherein the metalcomponents are mainly a platinum complex.
 21. The method ofmanufacturing a metal or metal compound pattern as claimed in claim 1,wherein as the metal components, at least any one of elemental forms ofrhodium, bismuth, ruthenium, vanadium, chromium, tin, lead and siliconor a compound thereof is contained.
 22. A method of manufacturing anelectron source provided with a plurality of electron-emitting deviceshaving an electrode, wherein the electrode is manufactured by a methodcomprising: a coating step of coating a photosensitive resin ofnegative-type on a surface of a substrate, the resin having watersoluble characteristics; an exposing step of exposing the coatedphotosensitive resin to a light with a mask; a removing step of removinga light-unexposed portion of the coated photosensitive resin andmaintaining a light-exposed portion which forms a resin patterncorresponding to the metal or metal compound pattern by developing thephotosensitive resin subjected to the exposing step with a developingwater solution; subsequent to the pattern forming step, an absorbingstep of making the resin pattern absorb a water solution containingmetal components; and a burning step of burning the resin pattern thathas absorbed the solution containing metal components, to remove a resincomponent therefrom and maintain patterned metal components thereonwhich become the electrode, wherein performance of said absorbing stepmakes the resin pattern absorb an amount of the water solutioncontaining metal components sufficient to form the electrode to have athickness of 15 nm to 78 nm.